Acid blend for removing etch residue

ABSTRACT

A method for removing organometallic and organosilicate residues remaining after a dry etch process from semiconductor substrates. The substrate is exposed to a conditioning solution of a fluorine source, a non-aqueous solvent, a complementary acid, and a surface passivation agent. The fluorine source is typically hydrofluoric acid. The non-aqueous solvent is typically a polyhydric alcohol such as propylene glycol. The complementary acid is typically either phosphoric acid or hydrochloric acid. The surface passivation agent is typically a carboxylic acid such as citric acid. Exposing the substrate to the conditioning solution removes the remaining dry etch residues while minimizing removal of material from desired substrate features.

FIELD OF THE INVENTION

The present invention relates to the fabrication of semiconductordevices and more particularly to a method for cleaning a semiconductorsubstrate after the formation of dry etch residues thereon.

BACKGROUND OF THE INVENTION

The importance of minimizing contamination during semiconductorfabrication processes has been recognized since the early days of theindustry. As semiconductor devices have become smaller and more complex,cleanliness requirements have become increasingly stringent, especiallyfor devices with submicron critical dimensions, because the ability toreliably create multi-level metallization structures is increasinglyvital. The importance of cleaning and conditioning steps during thedevice fabrication process is also emphasized because small-scaleresidues that may not have seriously affected the performance of deviceswith large geometries may result in disabling defects in submicrondevices.

Dry etch processes play a key role in developing multi-levelmetallization structures on semiconductor substrates. The step oftransferring the desired pattern from the photoresist into the substrateis often accomplished via a dry etch process. While dry etch processesare effective for selectively etching the substrate in only the areasnot masked by photoresist, these processes have a tendency to leavebehind residues on the substrate. Although these residues may serve abeneficial role during a dry etch process, they are undesirable afterthe completion of the dry etch process. In back end of the lineprocesses, where both dielectrics, such as SiO₂, and metals, such as Alor W, are present, the residues left behind by dry etch processes mayinclude both organometallic and organosilicate species. Theseundesirable post-etch residues are often difficult to remove withoutdamaging the desired substrate features.

Current methods for removing dry etch residues have met with onlylimited success. Traditional cleans involving aqueous acid solutions cannot provide a general solution for removing these residues, as theseprocesses are not suitable for processing in the presence of metallines. Current strategies often involve treating substrates withsolutions containing hydroxylamine (NH₂OH) and an organic chelatingagent. These methods have shown some effectiveness but have significantdrawbacks. These types of solutions can cause corrosion of exposed metalon the wafer and usually require long processing times at temperaturesnear 100 C. These hydroxylamine solutions are also expensive, as thechemicals are not only expensive to purchase but also typically requirespecialized disposal.

As the removal of dry etch residues grows increasingly troublesome inmicroelectronic device manufacture, there is a need for an effectivemethod of removal of these residues which can be easily implemented instandard wafer processing equipment and has reduced costs for chemicalpurchase and disposal.

SUMMARY OF THE INVENTION

The present invention provides an adaptable method for removingorganometallic, organosilicate, and other residues from a semiconductorsubstrate following a dry etch process. A substrate previously subjectedto a dry etch process is exposed to a conditioning solution to removeresidues remaining after the dry etch. The composition of theconditioning solution can be varied to match specific applications. Theconditioning solution generally contains a source of fluorine, acomplementary acid, a non-aqueous solvent, and preferably a surfacepassivation agent. One group of preferred conditioning solutions aresolutions composed of HF, H₃PO₄, a polyhydric alcohol such as propyleneglycol, and a surface passivation agent such as citric acid. In analternate group of preferred embodiments the conditioning solutions arecomposed of HF, HCl, a polyhydric alcohol, and a surface passivationagent. The substrate is exposed to the conditioning solution for asufficient amount of time to remove the undesired residues. Afterexposing the substrate to the conditioning solution, the substrate isrinsed, preferably by exposing the substrate to a rinse bath of a mildlyacidic aqueous solution. Preferably this rinse step also involvesbubbling a gas through the rinse bath to agitate the rinse bath.

Additional advantages and features of the present invention will beapparent from the following detailed description and drawings whichillustrate preferred embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of a substrate with dry etchresidues near a sample device feature.

FIG. 2 is a schematic cross-sectional view of a substrate undergoing theprocess of a preferred embodiment of the invention.

FIG. 3 shows the substrate of FIG. 2 at a processing step subsequent tothat shown in FIG. 2.

FIG. 4 shows the substrate of FIG. 2 at a processing step subsequent tothat shown in FIG. 3.

FIG. 5 shows the substrate of FIG. 2 at a processing step subsequent tothat shown in FIG. 4.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In the following detailed description, reference is made to theaccompanying drawings which form a part hereof, and in which is shown byway of illustration specific embodiments in which the invention may bepracticed. These embodiments are described in sufficient detail toenable those skilled in the art to practice the invention, and it is tobe understood that structural and chemical changes may be made withoutdeparting from the spirit and scope of the present invention.

The terms “wafer” and “substrate” are to be understood as including anysemiconductor-based structure having an exposed layer which may beeffectively cleaned by the process of the present invention. Typicallythis will include semiconductor-based structures which have beendry-etched and have resultant organometallic and/or organosilicateresidues on an exposed layer, but other structures may also bebeneficially treated by the present inventive method. “Wafer” or“substrate” may include silicon-on-insulator (SOI) orsilicon-on-sapphire (SOS) technology, doped and undoped semiconductors,epitaxial layers of silicon supported by a base semiconductorfoundation, and other semiconductor structures. Furthermore, whenreference is made to a “wafer” or “substrate” in the followingdescription, previous process steps may have been utilized to formregions or junctions in the base semiconductor structure or foundation.In addition, the semiconductor need not be silicon-based, but could bebased on silicon-germanium, germanium, or gallium arsenide.

The following detailed description is, therefore, not to be taken in alimiting sense, and the scope of the present invention is defined by theappended claims. When referring to solutions described herein, the term“percent” refers to the percent measured by weight, e.g., a 90% aceticacid solution is 90% by weight acetic acid.

Referring now to the drawings, where like elements are designated bylike reference numerals, FIG. 1 depicts a semiconductor wafer 20 in anintermediate processing stage of a fabrication process. The wafer 20comprises a substrate 22 with devices 24 located thereon. The devices 24are covered by a dielectric layer 26 of SiO₂, BPSG, or other suitablematerial which has a top surface 28. A device feature that has beenformed by a dry etch process is formed on the substrate 22, either on orin the dielectric layer 26. For exemplary purposes, the device featurewill be illustrated and described as a trench 30 which may be a via, butit should be understood that the invention is not limited thereto.

The trench 30 is formed in the dielectric material, and has sidewalls 32and a bottom surface 34. If trench 30 represents an unfilled viaallowing connection between metal levels, the bottom surface 34 may becomposed of a metal such as aluminum or tungsten. The wafer 20 of FIG. 1has been subjected to a dry etch process followed by a photoresistashing or stripping process. Due to the dry etch process, residues 40,which may be, for example, organosilicate or organometallic residues,are present on the top surface 28 of the dielectric layer 26 and on thesidewalls 32 of the trench 30. If not removed, the residues 40 couldprevent proper deposition of subsequent layers in the trench 30 or onthe dielectric layer 26.

An embodiment of the present invention for removing residues isillustrated by FIGS. 2 through 5. This embodiment uses a conditioningsolution to cleanse the substrate surface after performance of a dryetch. The substrate 22 is exposed to the conditioning solution for aperiod of time sufficient to remove residues 40 from the substratesurface while minimizing the amount of material removed from exposedsurfaces, such as metal lines, vias, or dielectric layers. Thecomposition of the conditioning solution can be varied to match specificapplications. The conditioning solution generally contains a fluorinesource, a complementary acid, and a non-aqueous solvent. Thecomplementary acid may be H₃PO₄, HCl, or another acid or combination ofacids which can serve as a pH suppressant. The non-aqueous solvent maybe a polyhydric alcohol, such as propylene glycol or ethylene glycol.Alternatively, the non-aqueous solvent may be one of many other suitableorganic solvents, including tetrahydrofuran, dimethylsulfoxide,propylene carbonate, or isopropyl alcohol. The conditioning solutionpreferably also contains a surface passivation agent. The surfacepassivation agent may be a carboxylic acid, such as citric acid, aceticacid, or EDTA. Other organic acids which are not carboxylic acids mayalso be suitable, such as ascorbic acid. Preferred conditioningsolutions are solutions of HF, H₃PO₄, and a polyhydric alcohol such aspropylene glycol; solutions of HF, H₃PO₄, a polyhydric alcohol, and asurface passivation agent; solutions of HF, HCl, and a polyhydricalcohol; and solutions of HF, HCl, a polyhydric alcohol, and a surfacepassivation agent such as citric acid.

Although HF is the preferred fluorine source, other fluorine sources maybe effectively employed within the scope of this invention. For example,NH₄F might be employed as the fluorine source as long as the NH₄F wascompatible with the other components selected for the conditioningsolution. Similarly, H₃PO₄ is not the only source of phosphatecontemplated within the inventive method. For example, phosphate saltswhich could dissociate to yield H₂PO₄ ⁻, HPO₄ ² ⁻, or PO₄ ³ ⁻ might beappropriate depending on the other components in the conditioningsolution. HF and H₃PO₄, however, are particularly preferred andconvenient choices for the fluorine source and the complementary acid.

Referring to FIG. 2, the process of the present invention beginssubsequent to the formation of devices 24, which may be transistors,capacitors, word lines, bit lines, or the like, on a substrate 22 of awafer 20 and the formation of a dielectric layer 26 on the substrate 22.The dielectric layer 26 may be a silicon dioxide, borophosphosilicateglass (BPSG), phosphosilicate glass (PSG), borosilicate glass (BSG) orother dielectric layer, and may be deposited by chemical vapordeposition or other suitable means.

FIG. 3 depicts the next step of the process, in which a photoresist 42is formed on the top surface 28 of the dielectric layer 26 by suitablemeans such as a spin-on technique. The photoresist 42 is patterned anddeveloped, and a dry etch process is performed on the substrate usingthe patterned photoresist as an etch mask. At the end of the dry etchprocess, residues 40 are left behind on the substrate. FIG. 4 depictstwo possible locations where the residues might reside on the substrateonce the remaining photoresist is removed by a suitable process such asashing or stripping. Residues 40 might remain on the top surface 28 ofthe dielectric layer 26, or inside the trench 30, as shown in FIG. 4, orpotentially at other locations on the wafer.

The wafer 20 is then subjected to the cleansing process of the presentinvention. The wafer 20 is exposed to a conditioning solution by anysuitable method, which is typically a wet processing method. Suitablemethods may involve immersion of the wafer 20, either singly or incombination with other wafers, into a bath containing the conditioningsolution, or by dispensing of the conditioning solution onto one or morewafers 20 as a stream or spray, so long as such dispensing of theconditioning solution results in exposure of the surface of thesubstrate to the conditioning solution for the desired length of time.Other methods of treating substrates with the conditioning solution willbe apparent to those skilled in the art. The wafer 20 is exposed to theconditioning solution for a time sufficient to remove residues 40 fromthe top surface 28 of the dielectric layer 26 and from the sidewalls 32and bottom surface 34 of the trench 30. Residues 40 may beorganometallic residues, organosilicate residues, other post-etchresidues, or a combination of these residues. The cleansing method ofthis invention is effective for removal of these residues when presentindividually or in combination.

The wafer 20 may then be rinsed to prepare the substrate for asubsequent process step. In one embodiment, the substrate is rinsed withdeionized water. In a preferred embodiment, the substrate may be exposedto an acidic rinse composed of an aqueous solution of a suitable acid.Carboxylic acids such as citric acid, acetic acid, or EDTA (ethylenediamine tetraacetic acid) are preferred for this embodiment. Otherorganic acids which are not carboxylic acids may also be used, such asascorbic acid.

In another embodiment, the aqueous acid solution may be buffered toraise the pH of the solution to any desired pH level up to approximatelypH 8. In yet another embodiment, anti-etch agents may be added to therinse bath, such as ammonium lactate or boric acid. In anotherembodiment, the substrate may be rinsed by exposing the wafer to anorganic solvent, such as an alcohol, a polyhydric alcohol (such aspropylene glycol), a ketone, or a fluorocarbon. In another embodiment,the rinse may be carried out in a bath and the rinse bath may beagitated by introduction of a gas. The agitating gas may be CO₂, N₂, orother gases which can be conveniently introduced into the rinse bath foragitation. In yet another embodiment, the solution may be agitated usingmegasonic energy. In still another embodiment, the solution may beagitated by manual or robot-controlled shaking of the vessel containingthe rinse bath.

Use of the acidified rinse or buffered rinse greatly reduces thepotential for unwanted consumption of the desired substrate materialsafter exposing the wafer to the conditioning solution. In embodimentswhere rinsing is accomplished with a rinse bath, a gas may be bubbledthrough the rinse bath. When the gas is CO₂, introduction of the gasprovides another means for acidifying the rinse water as well due to theformation of carbonic acid. When the rinse is already acidified,however, inert gases such as N₂ exhibit similar effectiveness to CO₂. Insome applications of this method, either the wafer may not besusceptible to the unwanted consumption of the substrate or additionalloss of substrate material may not be critical. In these cases the wafermay be rinsed with deionized water.

In still another embodiment, the wafer 20 may be pre-rinsed with anon-aqueous solvent prior to the rinse step. In one embodiment, thenon-aqueous solvent is a polyhydric alcohol, such as propylene glycol.In another embodiment, the wafer is pre-rinsed with the same non-aqueoussolvent used in the conditioning solution. After pre-rinsing the waferwith a non-aqueous solvent, the wafer may be rinsed with any of therinses described above.

The exact nature and length of the rinse step may vary depending on thenext process step the substrate will undergo. The wafer 20 may bespin-dried after rinsing, if appropriate. The final structure of thewafer 20 with the residue removed is shown in FIG. 5. Further steps tocreate a functional circuit from the wafer 20 may now be carried out.

Typically the conditioning solution is composed of a fluorine source, acomplementary acid, a non-aqueous solvent, and a surface passivationagent. The fluorine source may be HF, NH₄F, or other suitable chemicalswhich can act as fluorine sources in the conditioning solution. Thenon-aqueous solvent is typically a polyhydric alcohol, such as propyleneglycol or ethylene glycol. Other organic solvents may also be used, suchas tetrahydrofuran, dimethylsulfoxide, propylene carbonate, or isopropylalcohol. In many embodiments, propylene glycol is preferred due toconsiderations of low health exposure risk and ease of disposal. Blendsof more than one alcohol may also be used. The complementary acid may beH₃PO₄, HCl, or another acid or combination of acids which may act as apH suppressant. Preferably, the acid or combination of acids selected asthe pH suppressant should be able to reduce the pH of the solution tobelow pH 2. The surface passivation agent is typically a carboxylicacid. Preferred carboxylic acids include citric acid, acetic acid, orEDTA. Other organic acids which are not carboxylic acids may also beused, such as ascorbic acid. Other surface passivation agents will beapparent to those skilled in the art. Other surface passivation agentscould generally include chelants or reducing agents.

In one series of embodiments, the conditioning solution is composed ofHF as the fluorine source, propylene glycol as the non-aqueous solvent,H₃PO₄ as the complementary acid, and citric acid as the surfacepassivation agent. In one embodiment, the conditioning solution iscomposed of approximately 0.01 percent to approximately 5.0 percent HF,approximately 80 percent to approximately 95 percent propylene glycol,approximately 1 percent to approximately 15 percent H₃PO₄, andapproximately 0.001 percent to approximately 1.0 percent citric acid. Ina preferred embodiment, the conditioning solution is composed ofapproximately 0.25 percent to approximately 0.3 percent HF,approximately 89 percent to approximately 94 percent propylene glycol,approximately 6 percent to approximately 7 percent H₃PO₄, andapproximately 0.09 percent to approximately 0.50 percent citric acid. Ina particularly preferred embodiment, the conditioning solution iscomposed of approximately 0.27 percent HF, approximately 91.5 percentpropylene glycol, approximately 6.5 percent H₃PO₄, and approximately0.25 percent citric acid.

In the above conditioning solutions the balance of the solution weightis made up by water. In many embodiments the conditioning solution isprepared by combining stock acid solutions which contain water, so asmall amount of water may be present in the conditioning solution. It ispreferred, however, that the water content of the conditioning solutionbe as low as possible.

In another series of embodiments, the conditioning solution is preparedby choosing HF as the fluorine source, HCl as the complementary acid,propylene glycol as the non-aqueous solvent, and citric acid as thesurface passivation agent. In an embodiment, the conditioning solutionis composed of approximately 0.01 percent to approximately 5.0 percentHF, approximately 80 percent to approximately 99 percent propyleneglycol, approximately 0.003 percent to approximately 1.0 percent HCl,and approximately 0.001 percent to approximately 1.0 percent citricacid. In a preferred embodiment, the conditioning solution is composedof approximately 0.25 percent to approximately 0.3 percent HF,approximately 90 percent to approximately 98 percent propylene glycol,approximately 0.005 percent to approximately 0.009 percent HCl,andapproximately 0.09 percent to approximately 0.5 percent citric acid. Ina particularly preferred embodiment, the conditioning solution iscomposed of approximately 0.27 percent HF, approximately 97.5 percentpropylene glycol, approximately 0.006 percent HCl, and approximately0.25 percent citric acid.

Once again, the balance of the solution weight in the above conditioningsolutions is made up by water. In many embodiments, the conditioningsolution is prepared by combining stock acid solutions which containwater, so a small amount of water may be present in the conditioningsolution. It is preferred, however, that the water content of theconditioning solution be as low as possible.

In another series of embodiments, the surface passivation agent may beomitted from the conditioning solution. The conditioning solution willstill effectively remove any organometallic, organosilicate, and otherpost-etch residues if the surface passivation agent is omitted. In theseembodiments, however, the risk of damage to features on the surface ofthe substrate is substantially increased. While these embodiments may beeffectively employed, greater care must be taken with other reactionparameters such as processing time and temperature in order to avoidpotential damage to desired surface features or the substrate.

Residue removal with the conditioning solution may be performed attemperatures of approximately 5 to approximately 60 degrees Celsius.Temperatures below 5 degrees Celsius may be used, but are not asfavorable due to decreased residue removal speeds. As a result, at lowertemperatures the conditioning solution may need to be applied to thesubstrate for longer periods of time, leading to lower throughput in aproduction setting. Temperatures above 60 degrees Celsius may also beused. Preferably, the substrate is exposed to the conditioning solutionat a temperature of approximately 35 to approximately 40 degreesCelsius. Exposing the substrate to the conditioning solution at atemperature of approximately 38 degrees Celsius is a particularlypreferred embodiment of this invention.

Preferably, the substrate is exposed to the conditioning solution for aperiod of time sufficient to remove any undesirable dry etch residuesfrom the surface of the substrate. This may involve an exposure of thesubstrate to the conditioning solution for periods of time ranging fromabout 10 seconds to about 60 seconds or longer depending on the exactnature of the substrate and the process temperature. Longer exposuretimes, such as about 180 seconds or longer, allow for greater removalefficiency of the dry etch residues but will also lead to lowerthroughput in a production setting. Also, depending on the exact natureof the substrate, longer exposures to the conditioning solution mayeventually lead to removal of material from exposed features on thesurface of the substrate, such as metal lines, vias, or dielectricsurfaces. As a result, the optimal amount of time for exposure of asubstrate to the conditioning solution will be substrate dependent. Thepreferred exposure time could be near 10 seconds, near 60 seconds, near180 seconds, or a longer or shorter period of time depending on theexact nature of the target substrate as well as the residues targetedfor removal.

The substrate may be treated with the conditioning solution by immersingthe substrate in a bath of the conditioning solution. Alternatively, thesubstrate may be treated with the conditioning solution by dispensingthe solution on to the substrate, such as by a spray technique. Othermethods for exposing the substrate to the conditioning solution will beapparent to those skilled in the art.

Without being bound by any particular theory, it is currently believedthat several factors contribute to the effectiveness of this method forremoving dry etch residues. It is believed that the carboxylic acid orother organic acid plays a role by passivating the surface of exposedmetal lines, especially aluminum lines, which are on the surface of thesubstrate. In embodiments where the conditioning solution includesphosphoric acid, it is believed that the H₃PO₄ and HF play complementaryroles of aiding in the removal of organometallic and organosilicateresidues, respectively. In embodiments where a pH suppressant ispresent, it is believed that the low pH of the conditioning solutiontends to allow hydrofluoric acid present in the solution to exist asmolecular HF and H₂F₂, as opposed to undergoing dissociation into H⁺,F⁻, HF²⁻, or any of the other likely species produced when HFdissociates in solution. By preventing dissociation of the HF present inthe conditioning solution, the HF is forced to remain in its molecularform which generally reacts much more slowly with substrate materialssuch as SiO₂ or the aluminum lines likely to be exposed on a substratesurface.

An alternate theory which could explain the lack of reactivity with thealuminum lines is that the nature of the conditioning solutionsuppresses the solubility of aluminum fluoride. Aluminum fluoride is oneof the likely products of any reaction involving aluminum lines on thesurface of the substrate. Lowering the solubility of aluminum fluoridemight cause this reaction product to build up at the surface of thealuminum lines and prevent further reaction.

As can be seen from the embodiments described herein, the presentinvention encompasses processes of removing dry etch residues fromsubstrates having exposed areas of metal and/or dielectric. In oneembodiment the substrate is treated with/exposed to an conditioningsolution composed of a fluorine source such as HF, a non-aqueoussolvent, which is typically a polyhydric alcohol such as propyleneglycol, a complementary acid, which could include H₃PO₄, HCl, or otherpH suppressants, and a surface passivation agent, which is typically acarboxylic acid such as citric acid. The conditioning solutionefficiently removes organometallic, organosilicate, and other dry etchresidues with minimal impact on exposed features on the substratesurface.

The above description and drawings are only illustrative of preferredembodiments which achieve the objects, features and advantages of thepresent invention. It is not intended that the present invention belimited to the illustrated embodiments. Any modification of the presentinvention which comes within the spirit and scope of the followingclaims should be considered part of the present invention.

What is claimed as new and desired to be protected by Letters Patent ofthe United States is:
 1. A method for processing a semiconductorsubstrate, the method comprising: performing a dry etch process on saidsemiconductor substrate; and removing dry etch residues from saidsemiconductor substrate by exposing said semiconductor substrate to aconditioning solution, wherein the conditioning solution comprises: afluorine source, a complementary acid, a non-aqueous solvent selectedfrom the group consisting of tetrahydrofuran, propylene carbonate, andblends thereof, and a surface passivation agent comprising ethylenediamine tetraacetic acid or ascorbic acid; wherein said conditioningsolution is substantially free of water, and said fluorine source, saidcomplementary acid, said non-aqueous solvent and said passivation agentare present in said conditioning solution in concentrations suitable forthe selective removal of said residues relative to any exposed metal onsaid semiconductor substrate.
 2. The method of claim 1, wherein thefluorine source is HF.
 3. The method of claim 1, wherein the fluorinesource is NH₄F.
 4. The method of claim 1, wherein the complementary acidis H₃PO₄.
 5. The method of claim 1, wherein the complementary acid is aphosphate salt.
 6. The method of claim 1, wherein the complementary acidis HCl.
 7. The method of claim 1, wherein the complementary acid is a pHsuppressant.
 8. The method of claim 1, wherein the surface passivationagent contributes to said selective removal by said solution bypassivating any exposed metal on said semiconductor substrate.
 9. Themethod of claim 1, wherein the fluorine source contributes to saidselective removal by said solution by substantially remaining inmolecular form.
 10. The method of claim 9, wherein the complementaryacid is present in sufficient amount to contribute to said fluorinesource substantially remaining in molecular form.
 11. The method ofclaim 1, wherein the non-aqueous solvent is tetrahydrofuran.
 12. Themethod of claim 1, wherein the fluorine source, the complementary acid,the non-aqueous solvent, and the surface passivation agent are presentin said solution in sufficient concentrations to suppress the solubilityof aluminum fluoride.
 13. The method of claim 1, wherein the non-aqueoussolvent is propylene carbonate.
 14. The method of claim 1, wherein thefluorine source is an organosilicate-removing agent and thecomplementary acid is an organometallic-removing agent.
 15. The methodof claim 1, wherein the fluorine source is HF and the complementary acidis HCl.
 16. The method of claim 1, wherein the surface passivation agentis ascorbic acid.
 17. The method of claim 1, wherein the surfacepassivation agent comprises a chelant.
 18. The method of claim 1,wherein the surface passivation agent comprises a reducing agent. 19.The method of claim 1, wherein said act of removing comprises exposingsaid substrate at a temperature within the range of approximately 5 toapproximately 60 degrees Celsius.
 20. The method of claim 1, whereinsaid act of removing comprises exposing said substrate at a temperaturewithin the range of approximately 35 to approximately 40 degreesCelsius.
 21. The method of claim 1, wherein said act of removingcomprises exposing said substrate at a temperature of approximately 38degrees Celsius.
 22. The method of claim 1, wherein said act of removingfurther comprises immersing the substrate in the conditioning solution.23. The method of claim 1, wherein said act of removing furthercomprises dispensing the conditioning solution onto the substrate. 24.The method of claim 1, wherein said act of removing comprises exposingsaid substrate for a time sufficient to remove substantially all dryetch residues from the substrate.
 25. The method of claim 1, whereinsaid act of removing comprises exposing said substrate for approximately10 seconds or longer.
 26. The method of claim 1, wherein said act ofremoving comprises exposing said substrate for approximately 60 secondsor longer.
 27. The method of claim 1, wherein the complementary acid isH₃PO₄.
 28. The method of claim 1, wherein the complementary acid isphosphate.
 29. The method of claim 1, wherein the complementary acid isHCl.
 30. The method of claim 1, wherein the complementary acid is a pHsuppresant.
 31. The method of claim 1, wherein the conditioning solutionis comprised of approximately 0.01 to approximately 5.0percent-by-weight of the fluorine source, approximately 80 toapproximately 90 percent-by-weight of the non-aqueous solvent,approximately 1 to approximately 15 percent-by-weight of thecomplementary acid, and approximately 0.001 to approximately 1.0percent-by-weight of the surface passivation agent.
 32. The method ofclaim 1, wherein the conditioning solution is comprised of approximately0.01 to approximately 5.0 percent-by-weight of the fluorine source,approximately 80 to approximately 95 percent-by-weight of thenon-aqueous solvent, approximately 0.003 to approximately 1.0percent-by-weight of the complementary acid, and approximately 0.001 toapproximately 1.0 percent-by-weight of the surface passivation agent.33. The method of claim 1, wherein the fluorine source is HF and thecomplementary acid is H₃PO₄.
 34. The method of claim 33, wherein the HF,non-aqueous solvent, and H₃PO₄ are present in the conditioning solutionin thc approximate proportion of 0.01-5.0:80-95:1-15.
 35. The method ofclaim 33, wherein the HF, non-aqueous solvent, and H₃PO₄ are present inthe conditioning solution in the approximate proportion of0.25-0.3:89-94:6-7.
 36. The method of claim 33, wherein the HF,non-aqueous solvent, and H₃PO₄ are present in the conditioning solutionin the approximate proportion of 0.27:91.5:6.5.
 37. The method of claim15, wherein the HF, non-aqueous solvent, and HCl are present in theconditioning solution in the approximate proportion of0.01-5.0:80-99:0.003-1.0.
 38. The method of claim 15, wherein the HF,non-aqueous solvent, and HCl are present in the conditioning solution inthe approximate proportion of 0.25-0.3:93-98:0.005-0.009.
 39. The methodof claim 15, wherein the HF, non-aqueous solvent, and HCl are present inthe conditioning solution in the approximate proportion of0.27:97.5:0.006.
 40. The method of claim 33, wherein the HF, non-aqueoussolvent, H₃PO₄, and surface passivation agent are present in theconditioning solution in the approximate proportion of0.01-5.0:80-95:1-15:0.001-1.0.
 41. The method of claim 33, wherein theHF, non-aqueous solvent, H₃PO₄, and surface passivation agent arepresent in the conditioning solution in the approximate proportion of0.25-0.3:89-94:6-7:0.09-0.5.
 42. The method of claim 33, wherein the HF,non-aqueous solvent, H₃PO₄, and surface passivation agent are present inthe conditioning solution in the approximate proportion of0.27:91.5:6.5:0.25.
 43. The method of claim 15, wherein the HF,non-aqueous solvent, HCl, and surface passivation agent are present inthe conditioning solution in the approximate proportion of0.01-5.0:80-99:0.003-1.0:0.001-1.0.
 44. The method of claim herein theHF, non-aqueous solvent, HCl, and surface passivation agent are presentin the conditioning solution in the approximate proportion of0.25-0.3:93-98:0.005-0.009:0.09-0.5.
 45. The method of claim 15 whereinthe HF, non-aqueous solvent, HCl, and surface passivation agent arepresent in the conditioning solution in the approximate proportion of0.27:97.5:0.006:0.25.
 46. The method of claim 1, further comprisingrinsing the substrate after said act of removing.
 47. The method ofclaim 46, wherein said act of rinsing comprises exposing the substrateto deionized water.
 48. The method of claim 46, wherein said act ofrinsing comprises exposing the substrate to an aqueous acid solution.49. The method of claim 48, wherein the aqueous acid solution is asolution of a carboxylic acid.
 50. The method of claim 48, wherein theaqueous acid solution is a solution of citric acid.
 51. The method ofclaim 48, wherein the aqueous acid solution is a solution of EDTA. 52.The method of claim 48, wherein the aqueous acid solution is a solutionof acetic acid.
 53. The method of claim 48, wherein the aqueous acidsolution is a solution of an organic acid.
 54. The method of claim 48,wherein the aqueous acid solution is a solution of ascorbic acid. 55.The method of claim 48, wherein the aqueous acid solution is a solutionof carbonic acid.
 56. The method of claim 48, wherein the aqueous acidsolution is buffered to a pH between approximately 4.0 and approximately8.0.
 57. The method of claim 46, wherein said act of rinsing comprisesexposing the substrate to an organic solvent.
 58. The method of claim57, wherein the organic solvent is propylene glycol.
 59. The method ofclaim 46, wherein said act of rinsing comprises exposing the substrateto a solution containing an anti-etch agent.
 60. The method of claim 59,wherein the anti-etch agent is ammonium lactate.
 61. The method of claim59, wherein the anti-etch agent is boric acid.
 62. The method of claim46, wherein said act of rinsing further comprises immersing thesubstrate in a rinse bath.
 63. The method of claim 62, wherein said actof rinsing further comprises agitating the rinse bath.
 64. The method ofclaim 63, wherein the rinse bath is agitated with megasonic energy. 65.The method of claim 63, wherein the rinse bath is agitated by bubbling agas through the rinse bath.
 66. The method of claim 65, wherein CO₂ isbubbled through the rinse bath.
 67. The method of claim 65, wherein N₂is bubbled through the rinse bath.
 68. The method of claim 46, furthercomprising pre-rinsing the substrate with a second non-aqueous solventsubsequent to said act of removing but prior to said act of rinsing. 69.The method of claim 68, wherein the second non-aqueous solvent is apolyhydric alcohol.
 70. The method of claim 68, wherein the secondnon-aqueous solvent is propylene glycol.
 71. The method of claim 68,wherein the second non-aqueous solvent is the same non-aqueous solventused in the conditioning solution.
 72. A method for processing a wafer,the method comprising: performing a dry etch process on said wafer; andremoving at least one of organometallic and organosilicate residues ofsaid dry etch process from exposed surfaces of said wafer by treatingthe wafer with a conditioning solution comprising: a fluorine-containingorganosilicate-removing agent, a non-aqueous solvent selected from thegroup consisting of tetrahydrofuran, propylene carbonate, and blendsthereof, an organometallic-removing complementary acid, and a surfacepassivation agent comprising ethylene diamine tetraacetic acid orascorbic acid; wherein said conditioning solution is substantially freeof water, and said organosilicate-removing agent, saidorganometallic-removing complementary acid, said non-aqueous solvent andsaid passivation agent are present in said conditioning solution inconcentrations suitable for the selective removal of said residuesrelative to any exposed metal on said semiconductor substrate.
 73. Themethod of claim 72, further comprising rinsing the substrate after saidact of removing.
 74. The method of claim 72, wherein thefluorine-containing organosilicate-removing agent is HF and theorganometallic-removing complementary acid is HCl.
 75. The method ofclaim 74, where the HF, the non-aqueous solvent, the HCl, and surfacepassivation agent are present in the conditioning solution in theapproximate proportion 0.01-5.0:80-99:0.003-1.0:0.001-1.0.
 76. Themethod of claim 74, where the HF, the non-aqueous solvent, the HCl, andsurface passivation agent are present in the conditioning solution inthe approximate proportion 0.25-0.3:90-98:0.005-0.009:0.009-0.5.
 77. Themethod of claim 74, where the HF, the non-aqueous solvent, the HCl, andsurface passivation agent are present in the conditioning solution inthe approximate proportion 0.27:97.5:0.006:0.25.
 78. The method of claim72, wherein the fluorine-containing organosilicate-removing agent is HFand the organometallic-removing complementary acid is H₃PO₄.
 79. Themethod of claim 78, where the HF, the non-aqueous solvent, the H₃PO₄,and the surface passivation agent are present in the conditioningsolution in the approximate proportion 0.01-5.0:80-95:1-15:0.001-1.0.80. The method of claim 78, where the HF, the non-aqueous solvent, theH₃PO₄, and the surface passivation agent are present in the conditioningsolution in the approximate proportion 0.25-0.3:89-94:6-7:0.009-0.5. 81.The method of claim 78, where the HF, the non-aqueous solvent, theH₃PO₄, and the surface passivation agent are present in the conditioningsolution in the approximate proportion 0.27:91.5:6.5:0.25.
 82. Themethod of claim 72, wherein said act of removing comprises treating saidwafer at a temperature within the range of approximately 5 toapproximately 60 degrees Celsius.
 83. The method of claim 72, whereinsaid act of removing comprises treating said wafer at a temperaturewithin the range of approximately 35 to approximately 40 degreesCelsius.
 84. The method of claim is 72, wherein said act of removingcomprises treating said wafer at a temperature of approximately 38degrees Celsius.
 85. The method of claim 72, wherein said act ofremoving comprises treating said wafer for approximately 60 seconds orlonger.
 86. A method for processing a substrate with patternedphotoresist on the substrate surface comprising the steps of: providinga substrate with patterned photoresist on a surface of the substrate;performing a dry etch process on the substrate, wherein said dry etchprocess leaves at least one of organometallic and organosilicateresidues on said substrate; removing any remaining photoresist from thesurface of the substrate; and removing the dry etch residues from thesubstrate by exposing the substrate to a conditioning solution, saidconditioning-solution being a substantially water-free compositionsuitable for the selective removal of said residues relative to anyexposed metal on said semiconductor substrate and comprising: afluorine-containing organosilicate-removing agent, saidfluorine-containing organosilicate-removing agent-contributing to theselective removal by said conditioning solution by substantiallyremaining in molecular form; a non-aqueous solvent selected from thegroup consisting of tetrahydrofuran, propylene carbonate, and blendsthereof; an organometallic-removing complementary acid present insufficient amount to contribute to said fluorine-containingorganosilicate-removing agent substantially remaining in molecular form;and a surface passivation agent comprising ethylene diamine tetraaceticacid or ascorbic acid, said surface passivation agent contributing tothe selective removal by said conditioning solution by passivating saidany exposed metal on said semiconductor substrate.
 87. The method ofclaim 86, further comprising rinsing the substrate after said act ofremoving dry etch residues.
 88. The method of claim 86, wherein thefluorine-containing organosilicate-removing agent is HF and theorganometallic-removing complementary acid is HCl.
 89. The method ofclaim 88, where the HF, the non-aqueous solvent, the HCl, and thesurface passivation agent are present in the conditioning solution inthe approximate proportion 0.01-5.0:80-99:0.003-1.0:0.001-1.0.
 90. Themethod of claim 88, where the HF, the non-aqueous solvent, the HCl, andthe surface passivation agent are present in the conditioning solutionin the approximate proportion 0.25-0.3:90-98:0.005-0.009:0.009-0.5. 91.The method of claim 88, where the HF, the non-aqueous solvent, the HCl,and the surface passivation agent are present in the conditioningsolution in the approximate proportion 0.27:97.5:0.006:0.25.
 92. Themethod of claim 86, wherein the fluorine-containingorganosilicate-removing agent is HF and the organometallic-removingcomplementary acid is H₃PO₄.
 93. The method of claim 92, where the HF,the non-aqueous solvent, the H₃PO₄, and the surface passivation agentare present in the conditioning solution in the approximate proportion0.01-5.0:80-95:1-15:0.001-1.0.
 94. The method of claim 92, where the HF,the non-aqueous solvent, the H₃PO₄, and the surface passivation agentare present in the conditioning solution in the approximate proportion0.25-0.3:89-94:6-7:0.009-0.5.
 95. The method of claim 92, where the HF,the non-aqueous solvent, the H₃PO₄, and the surface passivation agentare present in the conditioning solution in the approximate proportion0.27:91.5:6.5:0.25.
 96. The method of claim 86, wherein said act ofremoving dry etch residues comprises exposing said substrate at atemperature within the range of approximately 5 to approximately 60degrees Celsius.
 97. The method of claim 86, wherein said act ofremoving dry etch residues comprises exposing said substrate at atemperature within the range of approximately 35 to approximately 40degrees Celsius.
 98. The method of claim 86, wherein said act ofremoving dry etch residues comprises exposing said substrate at atemperature of approximately 38 degrees Celsius.
 99. The method of claim86, wherein said act of removing dry etch residues comprises exposingsaid substrate for approximately 60 seconds or longer.
 100. A method fortreating a semiconductor substrate, the method comprising: performing adry etch process on said semiconductor substrate; and removing at leastone of organometallic and organosilicate residues of said dry etchprocess remaining on exposed surfaces of the substrate while minimizingthe removal of metal lines from said exposed surfaces by exposing thesubstrate to a substantially non-aqueous conditioning solutioncomprising HF, at least one of tetrahydrofuran or propylene carbonate,HCl, and at least one of ethylene diamine tetraacetic acid or ascorbicacid as a passivation agent in the approximate respectivepercentage-by-weight ratio 0.01-5.0:80-95:0.003-1.0:0.001-1.0.
 101. Amethod for treating a semiconductor substrate, the method comprising:performing a dry etch process on said semiconductor substrate; andremoving at least one of organometallic and organosilicate residues ofsaid dry etch process remaining on exposed surfaces of the substratewhile minimizing the removal of metal lines from said exposed surfacesby exposing the substrate to a substantially non-aqueous conditioningsolution comprising HF, at least one of tetrahydrofuran or propylenecarbonate, H₃PO₄, and at least one. of ethylene diamine tetraacetic acidor ascorbic acid as a passivation agent in the approximate respectivepercentage-by-weight ratio 0.01-5.0:80-90:1-15:0.001-1.0.
 102. A methodfor treating a semiconductor substrate, the method comprising:performing a dry etch process on said semiconductor substrate; removingat least one of organometallic and organosilicate residues of said dryetch process remaining on exposed surfaces of the substrate whileminimizing the removal of metal lines from said exposed surfaces byexposing the substrate to a substantially non-aqueous conditioningsolution comprising HF, at least one of tetrahydrofuran or propylenecarbonate, HCl, and at least one of ethylene diamine tetraacetic acid orascorbic acid as a passivation agent in the approximate respectivepercentage-by-weight ratio 0.25-0.3:90-98:0.0050-0.009:0.009-0.5; andrinsing the substrate.
 103. A method for treating a semiconductorsubstrate, the method comprising: performing a dry etch process on saidsemiconductor substrate; removing at least one of organometallic andorganosilicate residues of said dry etch process remaining on exposedsurfaces of the substrate while minimizing the removal of metal linesfrom said exposed surfaces by exposing the substrate to a substantiallynon-aqueous conditioning solution comprising HF, at least one oftetrahydrofuran or propylene carbonate, H₃PO₄, and at least one ofethylene diamine tetraacetic acid or ascorbic acid as a passivationagent in the approximate respective percentage-by-weight ratio0.25-0.3:90-94:6-7:0.009-0.5; and rinsing the substrate.